Monoazo dyestuffs



Patented Oct. 18, 1938 PATENT OFFICE MONOAZO DYESYTUFFS Richard Fleischhauer, Frankfort-on-the-Main Fechenheim, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing Applicationseptember so, 1936, Serial No. 103,363. In Germany October 2,

' lolaims. (o1. 260'163) This invention relates to valuable new monoazodyestuffs, more particularly to those of the general formula:

Y-om acyl 1 2 NHz Y-CH:

(wherein X, Y and Z have the above signification) with a coupling component.

The diazo components employed for the inanu facture of the dyestuffs of this invention 'have,

not hitherto been described. They mayb qb tained for example by acting 1 with ;1f-chloro:"lnitrobenzene 'or 1-chloro-4-nitrobenzenef2 sulfonic acid on' the corresponding aliphatic amines,

if necessary splitting off the sulfonic group, acylat ing the amino group and reducing th'e fnitro group. Thus, for example, i- (N-acetyl-isopropylamino) -4-aminobenzene may be prepared by heating 1-chloro-4-nitrobenzene2-sulfonic acid with an excess of isopropylamine in the presence of an aqueous solution of sodium carbonate in an autoclave to about C. for about 30 hours. The resulting 1-isopropylamin04nitr0benzene- 2-sulfonic acid is then treated with dilute'sul- 'furic acid in an autoclave at'about C. for

about" 20 hours so 'as to split 011 the sulfuric acid group. The yield thereof, which is about 85% of the theoretical} is subsequently acylated' by heating with acetic anhydri'de in the presence of a small amount of concentratedsulfuric acid,

whereby 1- (N-acetyl-isopropyl-amino)-4-nitrobenzene is formed with a very goodyield. Finally the nitro group of this compound is reduced in the usual manner by means of iron: and "acetic acid and 1-(N-acetyl-isopropyl-amino) 4-aminobenzene is obtained with a yield of about 75%. It crystallizes from benzine' in colorless crystals ,of 117 C. melting point.

In an analogous manner, l-(N-acetyl sec-butyL amino) -4-aminobenzene, 1- (N-benzoyl-isopropylamino) 4-aminobenzene, 1- (N-benzoyl-s'ec-butylamino) -4-nitrobenzene, and the like, may also be prepared.

The new dyestuffs are particularly useful for dyeing animal fibers. They are distinguished from the analogous dyestuffs notcontaining the following group:

acyl v in their diazo-component partly by clear more yellowish shades and partly by an increased levelling power. v

Example 1 19.2 parts of 1-(N-acetyl-isopropylamino)-4- aminobenzene are diazotized in the usual manner and the diazo solution obtained is allowed to run into a solution of 32- partsof '2-.naphthol-6;8--

disulfonic acid containing an excess of'sodium carbonate.

formula:

OH-N N=N son; I 1 H30 00 is isolated and dried. It forms a bright orange colored powder, soluble in water, dyeing wool and silk bright yellowish orange shades of good fastness to washing and light and of good levelling power.

By employing instead of the 2-naphthol-6.8- disulfonic acid other naphthol-mono-or-disulfonic acids such as per example 1-naphth0l-4-sulfonic acid, 1-naphthol-3-sulfonic acid, 2-naphthol-6- sulfonic acid, -1-naphthol-3.fiedisulfonic acid or 1 -naphthol-3.8-disulfonic acid dyestuifs are obtamed-which yield similar orange to yellowish red shades of likewise good levelling power.

Example 2 25.4 parts of 1-(N-benzoyl-isopropylamino)-4- aminobenzene are diazotized inthe usual manner and the diazo solution obtained is allowed to run into a solution of 37 parts of 1-acetylamino-8- naphthol-3.6-disulfonic acid containing an excess of sodium carbonate. When the combinationiscomplete the'dyestuifformed of the formula:

en r mo o 0 H3 Ha C The dyestuff thus obtained of the is-separated and dried. It is adark' red powder, soluble in water, dyeingwwool and silk bright bluish.

red shades of good levelling power and good fastness to fulling, light, seawater and perspiration.

Dyestufis of similar shades and fastn'ess properties are obtained by replacing the said diazo component by the corresponding amounts of l-(N- acetyl-isopropylamino) -4-aminobenzene, l-(N- acetyl-isopropylamino) -3-aminobenzene, 1'-(N methoxyacetyl-isopropyl-amino) 4 a min 0 ben zene, l- (N-acetyl-isopropylamino) -4-aminobenzene-2-sulfonic acid or of analogous amines which may contain any other acyl radicle.

By combining 1-(N-acetyl-isopropylamino) -4- aminobenzene-2-sulfonic acid with 2-amino'-8- naphthol-G-sulfonic acid in a medium containing a mineral acid a dyestuif is obtained which dyes wool bright red shades of good levelling power and excellent fastness to light.

Example 3 19.2 parts of 1-(N-acetyl-isopropylamino) -4- aminobenzene are diazotized in the usual manner and the diazo solution obtained is combined with 37 parts of l-acetylamino-8-naphthol-4.6-disulfonio acid. The dyestuff formed of the formula:

on lrlH-COCHa CHa /CHIII N=N' CH: CO

HOSS CH SOsH is isolated and dried. It is a dark 'red'powder, soluble in water, dyeing wool and silk brightred shades of good levelling power and fast to light. Example 4 19.2 parts of 1-(N-acetyl isopropylamino) -4- aminobenzene are diazotized in the'usual manner and the diazo solution obtained is combined with 26 parts of 1-(2' chloro-5'-sulfopheny1) -3-methy1-5-pyrazolone. The dyestuff formed of the is when" dry a lemon-yellow" powder,-soluble in water, dyeing wool and silk bright greenish yellow shades of very good levelling power and fastto washing and light.

Example 5 20.6 parts of 1-(N-acetyl-sec-butylamino) -4- aminobenzene are diazotized in the usual manner and the diazo solution obtained is allowed to run into a solution of 36 parts of l-benzdylamino-S- naphthol-l-sulfonic acid containing an excess of sodium acetate. When the combination iscomplete the dyestuff formed of the formula:

is isolated and dried. It is a brick-red powder, soluble in water, dyeing wool and silkbright yellowish red shades of very good levelling power and good fastness especially .to light.

The dyestufl! formed by employing 2-benzoylamino-5-naphthol-7-sulfonic acid as coupling component represents a yellowish red powder, soluble in water, dyeing wool and silk bright I orange shades of similar fastness properties.

Example 6 26.8 parts of -1- (N-benzoyl-sec-butylamino) -4- aminobenzene are diazotized in the usual manner and the diazo solution obtained is allowed to run at about 10-15 C. into a solution of 29 parts of 2-acetylamino-8-naphthol-6-sulfonic acid containing an excess of sodium acetate or sodium bicarbonate. When the combination is complete the dyestufi formed of the formula:

o H-lTI-C N=N -NHC o 0' H1 H10 CO is'isolated and dried. It is a red powder, soluble in water, dyeing wool and silk bright red shades of good levelling power and good fastness to fulling, light and perspiration. I

Dyestuifs of similar properties are obtained by employing other diazo components such as for example 1 (N benzenesulfo sec butylamino) 4 aminobenzene or 1-(N-p-toluenesulfo-isopropylamino) A aminobenzene.

There may be used as coupling components derivatives of 2-amino-8-naphthol-6-sulfonic acid, l-amino-S-naphthol-G-sulfonic acid, 1-amino-5- naphthol-l-sulfonicacid or 2-ar'nino-5-naphthol- '7-sulfonic acid containing other acyl radicles such as for example the methoxyacetyl, chloroacetyl, carbethoxya'cetyl, and phenoxyacetyl radicle and derivatives there'of substituted in the benzene nucleus. Furthermore, the acylamino-naphthalene-sulfonic acids "employed as coupling components may contain in their acyl'ated amine group aliphatic, hydroaro-v matic or aromatic radicles, by which the shades and properties of the 'dyestufis'obtained are I changed.

I'claim:

lfThe monoazo dyestufls' of the general formula:

x-om

Y CH acyl l wherein X and Y stand for 'members selected from the group consisting of hydrogen and methyl; acyl stands for an acyl radicle of the-aliphatic 'and'benzene'series Z stands-for a'member selected from the group consisting of hydrogenou lTIH-COKJH:

benzoyl, hexa-hydro-benzoyl.

which dyestufi represents a dark red powder, soluble in water, dyeing wool and silk bright bluish red shades of good levelling power and good fastness to fulling, light, seawater and per- 5 spiration.

3. The monoazo dyestufi of the formula:

HIC

/CHI?' N=Nfi-(|Z|LCH2 10 H10 00 110.0 N

CHI N 15 Hogswhich dyestuff represents a lemon-yellow powder, soluble in water, dyeing wool and silk bright greenish yellow shades of very good levelling power and fast to washing and light.

4. The monoazo dyestufi of the formula:

NH-CO RICHARD FLEISCHHAUER. 

